Carboxylate complexes alkylation

Alkene complexes Alkynyl complexes Ammine complexes Aqueous chemistry Arsine complexes Auranofin Auride ion Aurophilicity Binary compounds Bond lengths acetylacetonate complex alkyls and aryls ammine complexes carboxylates cyanide complexes dialkyl sulphide complexes dithiocarbamates to gold... 

It has been several decades since oxo-centered triruthenium-carboxylate complexes with triangular cluster frameworks of Ru3(p3-0)(p-00CR)6 (R = alkyl or aryl) were first isolated [1,2]. In the early 1970s, the first oxo-centered triruthenium complex was structurally characterized by Cotton through X-ray crystal structural determination [3]. Since then, oxo-centered trinuclear ruthenium-carboxylate cluster complexes with general formula [Ru30(00CR)6(L)2L ]n+ (R = aryl or alkyl, L and... 

Fig. 70. (Top) Carboxylate-functionalized alkyl and perfluoroalkyl ligands (bottom) benzoate and pentafluoro-benzoate ligands and their tris and ternary complexes.

Although heterobimetallic complexes with alkylated rare-earth metal centers were proposed to promote 1,3-diene polymerization via an allyl insertion mechanism, details of the polymerization mechanism and of the structure of the catalytically active center(s) are rare [58,83,118-125]. Moreover, until now, the interaction of the cationizing chloride-donating reagent with alkylated rare-earth metal centers is not well-understood. Lanthanide carboxylate complexes, which are used in the industrial-scale polymerization of butadiene and isoprene, are generally derived from octanoic, versatic, and... 

Scheme 22 [Carboxylate]- -[alkyl] exchange a mechanistic scenario of the formation of differently alkylated lanthanide carboxylate complexes (except for Ij, and I2 all Ln complexes were completely characterized ArR = C6H2R 3-2,4,6 or C6H3R 2-2,6) [148]...

Table 6 Polymerization of isoprene with bis-alkylated lanthanide carboxylate complexes [Ln(AlMe4)2(/x-02CArt"Bu)]2...

Cleavage of Ru—CH3 bonds by acids has been used by Werner et al. for the selective introduction of small molecules at the ruthenium center. Addition of HBF4 to complex 33, in the presence of carbon monoxide or ethylene, allows the coordination of these molecules in complexes 48,49, and 50 (43). Complexes of type 33 give carboxylate complexes 34,35, and 38 on treatment with carboxylic acids (42,43). A bis(alkyl)ruthenium(II) complex (52) was also obtained by addition of PMe3 to the ethylene complex 51 (24,26). 

The alkyl peroxide then can decompose to give PFe OH and 0=CR2, or, if a tertiary alkyl group, Acyl complexes such as PFe C(0)C4H9 react with dioxygen to yield only PFe carboxylate complexes and the fi-oxo dimer, PFe -0-Fe -P, with no evidence of ferryl complexes being formed. 

Pfizer reported the discovery of a new class of structurally complex alkyl carboxylic acids, as exemplified by CP-225917 and CP-263114 (Figure 20), that are weak and non-selective inhibitors of squalene synthase and FPTase. These compounds were isolated by acid base liquid-liquid partition, Sephadex LH20 chromatography and reverse phase HPLC from ethyl acetate extracts of an unidentified fungus that also produced zaragozic acid A [97]. 

Both irradiation by visible light and pyridine are required for the above insertion. The same carboxylate complexes can be prepared by reaction of acetic acid with either the alkyl(aryl)indium(III) porphyrins or the aquohydroxoindium(III) porphyrins. 

As for preformed cationic enolate complexes, one decomposition pathway has been conclusively identified. Enolates derived from 3° alkyl esters are prone to loss of alkene to form cationic carboxylate complexes (Scheme Since donors such as THF partially impede this process, prior coordination of the ester oxygen may precede elimination. By the same token, the unhindered enolate [Me2Si(77-G5Me4)(TuN)Zr 0G(0 Bu)=CMe2 (THF)][B G6H3(GF3)2 4] decomposes at temperatures above —20°G to form the cationic carboxylate complex, even in the presence of excess... 

L = [14]ane N4) haAre been used to make RS thiyl radicals, which in turn unexpectedly react with [EtCo(L)(H2P)]2+ to foim C2H4 and RSH.239-241 Addition of base to [(tacn)Co(L)] (tacn = 1,4,7-tiiazacyclononane L = l,6-diamino-3-thiahexane) causes deprotonation of L and formation of an N,C,N-bonded ligand, in equilibrium with its N,S,N-bonded fonn. > 3 other Co(III) alkyls have been produced by photochemical decarboxylation of chelate carboxylate complexes. The synthesis and structure of the nl-C 02 polymer [ Co(en)2(C02)) QO4 H20 ]n has been reported.246 The structure of [Co(salen)(Pr )(py)] has been determined,247 and tandem cyclisation reactions involving organocobalt salen and salophen complexes have been described.248.249... 

Interestingly, despite the fact that RCOMn(CO)s compounds decarbonylate easily, an attempt to eliminate CO2 from C2HsOOCMn(CO)5 was unsuccessful (59). Carbon dioxide elimination from carboxylate complexes to give alkyl or aryl derivatives has not been reported. 

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